CN109244355A - Preparation mends the method for the cathode of lithium, mends the cathode and lithium ion secondary battery of lithium - Google Patents
Preparation mends the method for the cathode of lithium, mends the cathode and lithium ion secondary battery of lithium Download PDFInfo
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- CN109244355A CN109244355A CN201710559663.0A CN201710559663A CN109244355A CN 109244355 A CN109244355 A CN 109244355A CN 201710559663 A CN201710559663 A CN 201710559663A CN 109244355 A CN109244355 A CN 109244355A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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Abstract
Provide a kind of cathode for mending lithium, the lithium ion secondary battery of preparation method and the cathode including the benefit lithium.The method that the cathode of lithium is mended in preparation includes: to form lithium film and/or lithium composite material film by vacuum coating in negative electrode material layer surface, and lithium amount of mending can be accurately controlled for different battery systems, and supplement battery forms the lithium of SEI film consumption, improves the capacity of battery.
Description
Technical field
The present invention relates to the field of lithium ion secondary battery more particularly to it is a kind of mend lithium cathode, preparation method and
The lithium ion secondary battery of cathode including the benefit lithium.
Background technique
In recent years, as the electric equipment products such as smart phone, tablet computer, electric car are to the need of high-energy-density electrochmical power source
It asks, the electrochmical power source of urgent need high-energy-density.Lithium ion secondary battery specific energy development space used at present is limited, passes through
The reason of specific energy of mode battery that cathode mends lithium can improve very much, and cathode benefit lithium can improve battery specific energy be battery for the first time
Cathode forms the lithium ion of solid electrolyte interface film (SEI film) consumption part when charging, and the coulomb of first charge-discharge is caused to be imitated
Rate is low, for example, carbon material coulombic efficiency for the first time 90% or so, the coulombic efficiency for the first time of silica-base material is 65%~85%.It adopts
The method for mending lithium with cathode, coulombic efficiency can improve 10%~20% or so for the first time, and lithium ion secondary battery specific energy obtains phase
The raising answered.
Have the report for the specific energy that lithium ion secondary battery is improved in such a way that cathode mends lithium, Chinese patent notification number
Organolithium spray solution or dropwise addition by the surface of negative electrode tab, being made the lithium ion in organolithium solution also by CN102916165A
Original obtains lithium metal, realizes that cathode mends lithium.The reagent of organolithium is more expensive, needs that object more stronger than lithium metal reproducibility is added
Lithium ion could be reduced into lithium metal by matter, increase cost, and the process route for mending lithium is complicated；China Patent Publication No.
CN104993098A mends the lithium source of lithium using lithium powder as cathode, and lithium powder particles are small, grain diameter micron order, exists when operation
The phenomenon that grain flies everywhere, very stringent to operating environment requirement, there are security risks.
Summary of the invention
For above-mentioned problems of the prior art, the present invention is intended to provide the negative of lithium is mended in a kind of simple and practical preparation
The method of pole can provide different benefit lithium amounts for different battery systems.
Above-mentioned purpose of the invention can be achieved through the following technical solutions.
According to an aspect of the present invention, a kind of method of the cathode of benefit lithium preparing lithium ion secondary battery, packet are provided
It includes: lithium film and/or lithium composite material film being formed by vacuum coating on the active material layer surface of cathode pole piece.
According to another aspect of the present invention, a kind of cathode for mending lithium is provided, is obtained by the above method.
According to a further aspect of the invention, a kind of lithium ion secondary battery is provided comprising the cathode of above-mentioned benefit lithium.
The benefit cathode of lithium obtained by the method for the invention, can be with batch application in lithium ion secondary battery, can be for difference
Battery system different benefit lithium amounts is provided, improve the specific energy of lithium ion secondary battery.Such as: be to mend the silicon carbon material of lithium
Cathode, nickel cobalt aluminium ternary material are the battery system of anode, and specific capacity can achieve the 174mAh/g (charge-discharge magnification of 0.2C
Under) more than.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the front view of the coiled benefit cathode of lithium of an embodiment according to the present invention.
Sectional view of the coiled benefit cathode of lithium along line A-A that Fig. 2 is Fig. 1.
Specific embodiment
Certain specific embodiments of the invention are described with reference to the accompanying drawing.It should be appreciated that not departing from this hair
In the case where bright range or spirit, those skilled in the art can imagine other various embodiments according to the introduction of the disclosure
And it can modify to it.Therefore, specific embodiment below does not have restrictive sense.
Unless otherwise specified, expression characteristic size, quantity and physical characteristic used in description and claims
All numbers be construed as to be modified by term " about " in all cases.Therefore, it is said unless there are opposite
Bright, the numerical parameter otherwise listed in specification and appended book is approximation, and those skilled in the art can
Seek the required characteristic obtained using teachings disclosed herein, suitably changes these approximations.The number indicated with endpoint
The use of value range include within the scope of this it is all number and any ranges within the scope of this, for example, 1 to 5 include 1,1.1,
1.3,1.5,2,2.75,3,3.80,4 and 5 etc..
In the description of the present invention, it is to be understood that, the orientation or positional relationship of the instructions such as term " on ", "lower" is base
In orientation or positional relationship shown in the drawings, it is merely for convenience of description of the present invention and simplification of the description, rather than indication or suggestion
Signified device or element must have a particular orientation, be constructed and operated in a specific orientation, therefore should not be understood as to this
The limitation of invention.
Fig. 1 shows the front view of the benefit cathode of lithium of an embodiment according to the present invention.The benefit cathode of lithium is coiled
Form, and be collector two sides coating method.There is negative electrode material layer 2 on the two sides of collector 3, have on negative electrode material layer 2
Lithium film or lithium composite material film 1.Sectional view of the coiled benefit cathode of lithium along line A-A that Fig. 2 is Fig. 1.It is pointed out that Fig. 1 and 2
The width of middle lithium film or lithium composite material film 1, negative electrode material layer 2 and collector 3 can arbitrarily be changed, not necessarily in ratio in figure,
But the width of lithium film or lithium composite material film 1 and negative electrode material layer 2 is no more than the width of collector 3.In addition, multiple forming lithium
In the case that condensation material film is used to mend lithium, lithium composite material film can have single layer structure (that is, single layer lithium composite material film),
It can have multilayered structure, for example, lithium layer/lithium composite bed of material, the lithium of the lithium layer/lithium composite bed of material/lithium layer or more layers
Layer/lithium composite bed of material alternating structure.
Collector for use in the present invention includes metal foil and carbon coating metal foil, for example, copper foil, nickel foil, carbon coating copper
Foil etc..Metal foil, such as the thickness of copper foil can be 5~10 microns.In carbon coating metal foil the thickness of carbon coating can for 1~
5 microns.
Negative electrode material layer can be formed on the single or double of collector by coating method.For example, can will contain
Negative electrode active material, conductive agent, binder and solvent slurry be applied on collector and form coating, obtain cathode material after dry
The bed of material.Wherein, negative electrode active material may include carbon material class negative electrode active material and silicon-based anode active material.Carbon material class
The example of negative electrode active material includes artificial graphite, natural graphite, soft carbon, hard carbon, carbonaceous mesophase spherules and graphene etc.；Silicon substrate
The example of negative electrode active material includes silicon carbon material, aoxidizes sub- silicon, aoxidizes sub- silico-carbo composite material, nano-silicon, nanometer silico-carbo
Composite material and silicon alloy etc..Conductive agent, binder and solvent are conductive agent commonly used in the art, binder and solvent, example
Such as, conductive agent may include acetylene black, Super P, carbon fiber, carbon nanotube, Ketjen black, graphene etc., and binder can wrap
Include PVDF (Kynoar), PTFE (polytetrafluoroethylene (PTFE)), CMC (carboxymethyl cellulose), polyimides, polyacrylic acid, seaweed
Sour sodium, SBR (styrene-butadiene) rubber, polyurethane etc., solvent may include NMP (N-Methyl pyrrolidone) etc..Cathode material
The thickness (thickness of single side negative electrode material layer) of the bed of material can be 0.030mm~0.15mm.
In the present invention, lithium film or lithium composite material film are formed on negative electrode material layer by vacuum coating.Certain
In embodiment, coiled cathode pole piece (including collector and can be formed in collector list by unreeling and wrap-up
Face or it is two-sided on negative electrode material layer) spread across vacuum coater, wherein by vacuum coating, on negative electrode material layer
Form lithium film or lithium composite material film.The thickness of lithium film or lithium composite material film can be 100 nanometers -15 microns, preferably 1~15
Micron.The multilayer film of lithium composite material can be formed by multiple plated film.
Lithium composite material for use in the present invention is the binary that lithium metal and at least one other elements are formed or polynary multiple
Condensation material, the other elements are selected from by aluminium element, magnesium elements, boron element, element silicon, phosphide element, Zn-ef ficiency, silver element, calcium
The group of element and manganese element composition.For example, lithium composite material may include the two of lithium metal and the formation of at least one other elements
Member or multicomponent alloy.Mass content of at least one other elements in lithium composite material is 0.1%~40%, preferably
1%~20%.
Vacuum coating can be 10-2~10-5It is carried out at a temperature of the vacuum degree of Pa and 500~1500 DEG C.Plated film time can
To be about 1~20 second.In vacuum evaporation composite material film, can be arranged in vacuum coater metal lithium source and one or
Multiple other elements sources heat metal lithium source (one or more other elements sources can also heat simultaneously), lithium metal are evaporated,
One layer of lithium film (thickness of lithium film can be several microns hereinafter, being, for example, less than 2 microns) is quickly plated on negative electrode material surface,
Then one or more other elements sources are heated up to evaporate other elements again.Due under high vacuum condition, the height of other elements
The evaporation rate of warm vapor atoms is than very fast, and penetration capacity is stronger, and when depositing on lithium film, some vapor atom can be penetrated into
It deposits among lithium film or on the surface, extremely strong, these vapor atoms and gold due to metallic lithium atoms activity and from welding performance
Belonging to lithium atom moment generates and is mutually dissolved, melts and cured process and lithium form lithium-other elements composite material film.It can also
To carry out lithium metal plated film again, lithium/other elements/lithium form composite material film is formed.
By the above-mentioned means, the present invention can accurately control lithium amount of mending for different battery systems, supplement battery forms SEI
The lithium of film consumption, improves the capacity of battery.
The following are some illustrative specific embodiments of the invention.
Specific embodiment 1 is a kind of method of the cathode of benefit lithium for preparing lithium ion secondary battery, which comprises
Lithium film and/or lithium composite material film are formed by vacuum coating in negative electrode material layer surface.
Specific embodiment 2 is the method according to specific embodiment 1, wherein the lithium film or lithium composite material
Film with a thickness of 100 nanometers -15 microns.
Specific embodiment 3 is the method according to specific embodiment 1, wherein the lithium composite material is metal
The binary or multi-element composite material that lithium and at least one other elements are formed, the other elements be selected from by aluminium element, magnesium elements,
The group of boron element, element silicon, phosphide element, Zn-ef ficiency, silver element, calcium constituent, manganese element composition.
Specific embodiment 4 is the method according to specific embodiment 3, wherein the lithium composite material includes gold
Belong to the binary or multicomponent alloy of lithium and the formation of at least one other elements.
Specific embodiment 5 is the method according to specific embodiment 3, wherein at least one other elements
Mass content in lithium composite material is 0.1%~40%, preferably 1%~20%.
Specific embodiment 6 is the method according to specific embodiment 1, wherein the vacuum coating is 10-2~
10-5It is carried out at a temperature of the vacuum degree of Pa and 500~1500 DEG C.
Specific embodiment 7 is the method according to specific embodiment 3, wherein the lithium composite material film is logical
First vacuum evaporation lithium metal, then at least one other elements described in vacuum evaporation are crossed, and optionally replaces vacuum evaporation again
Lithium metal, or optionally replace vacuum evaporation lithium metal and at least one other elements again and formed.
Specific embodiment 8 is the method according to specific embodiment 1, wherein the negative electrode material layer includes negative
Pole active material, the negative electrode active material include in carbon material class negative electrode active material and silicon-based anode active material at least
It is a kind of.
Specific embodiment 9 is the method according to specific embodiment 8, wherein the carbon material class negative electrode active
Material includes artificial graphite, natural graphite, soft carbon, hard carbon, carbonaceous mesophase spherules and graphene；The silicon-based anode activity material
Material includes silicon carbon material, aoxidizes sub- silicon, aoxidizes sub- silico-carbo composite material, nano-silicon, nano-silicon-carbon composite and silicon alloy.
Specific embodiment 10 is the method according to specific embodiment 1, wherein the cathode of the benefit lithium includes
Collector, the negative electrode material layer are formed on the single or double of the collector.
Specific embodiment 11 is the method according to specific embodiment 10, wherein the collector includes copper
Foil, nickel foil, carbon coating copper foil.
Specific embodiment 12 is the method according to specific embodiment 10, wherein the negative electrode material layer passes through
Slurry containing negative electrode active material, conductive agent, binder and solvent is applied on collector and is obtained.
Specific embodiment 13 is the method according to specific embodiment 1, wherein the cathode of the benefit lithium is into
Roll form or sheet.
Specific embodiment 14 is a kind of cathode for mending lithium, as according to any one of specific embodiment 1 to 13
Method obtain.
Specific embodiment 15 is a kind of lithium ion secondary battery comprising benefit lithium is negative described in specific embodiment 14
Pole.
Embodiment
Hereinafter, by embodiment, the present invention will be described in more detail, but these embodiments are merely exemplary, and should not be understood
For limitation of the scope of the invention.
Embodiment 1:
A prepares negative electrode material
By negative electrode active material artificial graphite (Tianjin Bei Terui New Energy Technology Co., Ltd.), binder PVDF is conductive
Agent acetylene black, in mass ratio 80:10:10 ratio are mixed into slurry in solvent NMP, by automatic coating machine, in coiled copper foil
Double spread slurry on collector, obtains cathode.
Cathode of lithium is mended in B preparation
The coiled cathode vacuum drying oven of preparation is dried, by winding and unwinding device, in vacuum coater,
10-2Pa pressure and 600~1200 DEG C of temperature obtain two-sided being coated with 2 microns of thick lithiums respectively in negative terminal surface vacuum evaporation lithium film
The cathode of film.
C charge and discharge comparative experiments
(1) using artificial graphite as negative electrode material, LiFePO4(Hunan Shanshan New Materials Co., Ltd) is as positive material
Material, electrolyte are 1mol/L LiPF6-EC/EMC (volume ratio 1:1, EC: ethylene carbonate, EMC: methyl ethyl carbonate, Dongguan China fir
China fir battery material Co., Ltd), with 0.2C rate charge-discharge, coulombic efficiency is 90.4% to battery for the first time.
(2) cathode is the artificial graphite for plating 2 microns thick lithium film, the other structures of battery and is formed as (1), battery
Discharge capacity improves for the first time, and coulombic efficiency is 97.9% for the first time.
Embodiment 2:
A prepares negative electrode material
Negative electrode active material nano-silicon (partial size 35nm, Beijing Deco Dao Jin Science and Technology Ltd.)/artificial graphite is compound
Material (wherein silicone content 10%), binder use PAA (polyacrylic acid), conductive agent: carbon black, in mass ratio 85:10:5 ratio
It is mixed into slurry in solvent NMP, by coating machine, negative electrode material on double spread, is born on coiled copper foil of affluxion body
Pole.
The cathode of lithium is mended in B preparation
Moisture will be dried in the coiled cathode vacuum drying oven of preparation, by winding/unwinding device, in vacuum coater,
10-2Pa pressure and 600~1200 DEG C of temperature obtain the 5 microns thick lithium films of two-sided plating respectively in negative terminal surface vacuum evaporation lithium film
Benefit cathode of lithium.
C charge-discharge test
(1) using nano-silicon/artificial graphite composite material as negative electrode material, NCM (nickel cobalt manganese) ternary material is as just
Pole material, electrolyte 1mol/L LiPF6-EC/DMC (volume ratio 1:1, EC: ethylene carbonate, DMC: dimethyl carbonate, Dongguan
Shan Shan battery material Co., Ltd), electrolysis additive: vinylene carbonate 2wt%, di-oxalate lithium borate 3wt%, three is thio
Ethylene carbonate 3wt%, with 0.2C rate charge-discharge, coulombic efficiency is 70.1% to battery for the first time.
(2) cathode using the 5 microns thick lithium films of plating nano-silicon/artificial graphite composite material, it is other with (1) unanimously, battery
Coulombic efficiency for the first time rise to 88.4%.
Embodiment 3:
With embodiment 2, except different from embodiment 2 below
A prepares negative electrode material
Active material is the composite material for aoxidizing sub- silicon (Tianjin Bei Terui New Energy Technology Co., Ltd.)/artificial graphite
(content for wherein aoxidizing sub- silicon is 20%)
The cathode of lithium is mended in B preparation
It obtains mending cathode of lithium being the two-sided cathode for plating 3 microns thick lithium film respectively.
The verifying of C charge-discharge test
(1) cathode is using oxidation Asia silicon/artificial graphite composite material of plating lithium film, and anode is using NCA (nickel cobalt aluminium) ternary
The additive and embodiment 2 of material, electrolyte and electrolyte are consistent, and with the rate charge-discharge of 0.2C, the coulomb for the first time of battery is imitated
Rate is 75%.
(2) for cathode using oxidation Asia silicon/artificial graphite composite material of 2 microns of plating thick lithium films, other and (1) is unanimously, electric
The coulombic efficiency for the first time in pond rises to 92%.
Embodiment 4:
A prepares cathode material
By active material artificial graphite, binder PVDF, conductive agent carbon black, 80:10:10 ratio in mass ratio is in solvent
Slurry is mixed into NMP, by automatic coating machine, double spread spreading mass, obtains cathode on coiled copper foil of affluxion body.
Cathode of lithium is mended in B preparation
The coiled cathode vacuum drying oven of preparation is dried, is obtained by winding and unwinding device by vacuum coating technology
The cathode of the two-sided lithium magnesium base composite material film (content of magnesium account for lithium magnesium total content 1%) for plating 1 micron thick respectively.
The specific preparation condition of lithium magnesium base composite material film is as follows: (1) in vacuum degree 10-2Under Pa pressure, in upstream and downstream
Two crucibles are set, and a crucible holds solid metallic lithium, and a crucible holds solid metallic magnesium；(2) heating of lithium ingot is set
Temperature is 600~1200 DEG C, heating crucible, and quickly plating a layer thickness on negative electrode material surface is 1 micron of lithium film；(3) adding
While thermometal lithium, the crucible for holding magnesium metal is also begun to warm up, and setting temperature is 500~1100 DEG C, what is plated
On lithium film, one layer of nanometer thickness magnesium membrane material is quickly plated, since under high vacuum condition, the volatilization of magnesium metal high-temperature steam atom is fast
For degree than very fast, penetration capacity is stronger, and when depositing on lithium film, part magnesium vapor atoms can be penetrated among lithium film or on surface
Upper deposition, extremely strong due to metallic lithium atoms activity and from welding performance, magnesium vapor atoms and metallic lithium atoms moment generate phase
Mutually dissolution, melting and cured process and lithium form lithium magnesium base composite material film.
C charge and discharge comparative experiments
(1) cathode uses artificial graphite, and anode uses LiCoO2Material (Hunan Shanshan New Materials Co., Ltd), electrolyte
For 1mol/L LiPF6-EC/DMC (volume ratio 1:1, EC: ethylene carbonate, DMC: dimethyl carbonate, Dongguan China fir China fir battery material
Co., Ltd), with 0.2C rate charge-discharge, coulombic efficiency is 89.2% to battery for the first time.
(2) cathode is using the artificial graphite of 1 micron of plating thick lithium magnesium base composite material film, and other as (1), battery is for the first time
Discharge capacity significantly improves, and coulombic efficiency is 98.1% for the first time.
Specific test data such as following table
Practical application of the invention is not limited to above-mentioned specific embodiment 1,2,3,4, and present invention may apply to institutes
Some lithium ion secondary battery systems.
Claims (10)
1. a kind of method of the cathode for the benefit lithium for preparing lithium ion secondary battery, which is characterized in that the described method includes: in cathode
Lithium film and/or lithium composite material film are formed by vacuum coating in material surface.
2. the method according to claim 1, wherein the lithium film or lithium composite material film with a thickness of 100
- 15 microns of nanometer.
3. the method according to claim 1, wherein the lithium composite material be lithium metal and it is at least one its
The binary or multi-element composite material that his element is formed, the other elements be selected from by aluminium element, magnesium elements, boron element, element silicon,
The group of phosphide element, Zn-ef ficiency, silver element, calcium constituent, manganese element composition；It is preferred that the lithium composite material include lithium metal with extremely
The binary or multicomponent alloy that a kind of few other elements are formed；It is preferred that at least one other elements are in lithium composite material
Mass content is 0.1%~40%, more preferable 1%~20%.
4. the method according to claim 1, wherein the vacuum coating is 10-2~10-5The vacuum degree of Pa and
It is carried out at a temperature of 500~1500 DEG C.
5. according to the method described in claim 3, it is characterized in that, the lithium composite material film is by first vacuum evaporation gold
Belong to lithium, then at least one other elements described in vacuum evaporation, and optionally replace vacuum evaporation lithium metal again, or optionally
Ground replaces vacuum evaporation lithium metal and at least one other elements again and is formed.
6. the method according to claim 1, wherein the negative electrode material layer includes negative electrode active material, institute
Stating negative electrode active material includes at least one of carbon material class negative electrode active material and silicon-based anode active material；It is preferred that described
Carbon material class negative electrode active material include artificial graphite, natural graphite, soft carbon, hard carbon, carbonaceous mesophase spherules and graphene；It is excellent
The choosing silicon-based anode active material includes silicon carbon material, aoxidizes sub- silicon, aoxidizes sub- silico-carbo composite material, nano-silicon, nanometer
Silico-carbo composite material and silicon alloy.
7. the method according to claim 1, wherein the cathode of the benefit lithium includes collector, the cathode
Material layer is formed in by the way that the slurry containing negative electrode active material, conductive agent, binder and solvent to be applied on collector
On the single or double of the collector；It is preferred that the collector includes copper foil, nickel foil, carbon coating copper foil.
8. the method according to claim 1, wherein the cathode of the benefit lithium is roll format or sheet.
9. a kind of cathode for mending lithium, is obtained by method according to any one of claim 1 to 8.
10. a kind of lithium ion secondary battery, including the cathode as claimed in claim 9 for mending lithium.
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| CN201710559663.0A CN109244355B (en) | 2017-07-11 | 2017-07-11 | Method for producing lithium-supplemented negative electrode, and lithium ion secondary battery |
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| CN201710559663.0A CN109244355B (en) | 2017-07-11 | 2017-07-11 | Method for producing lithium-supplemented negative electrode, and lithium ion secondary battery |
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| CN111430659A (en) * | 2019-11-27 | 2020-07-17 | 蜂巢能源科技有限公司 | Pre-lithiation treatment method for lithium ion battery cathode, lithium ion battery cathode and lithium ion battery |
| CN111560595A (en) * | 2020-03-30 | 2020-08-21 | 维达力实业(深圳)有限公司 | Returning type lithium supplementing method for silicon-containing negative electrode material, negative electrode piece and battery |
| CN111613771A (en) * | 2020-06-29 | 2020-09-01 | 蜂巢能源科技有限公司 | Battery cathode and preparation method and application thereof |
| WO2020207368A1 (en) * | 2019-04-11 | 2020-10-15 | 宁德时代新能源科技股份有限公司 | Lithium supplementing layer and negative pole piece thereof, lithium-ion battery and device |
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